Tetravalent Uranium and Thorium Complexes: Elucidating Disparate Reactivities of AnIVCl2 (An = U, Th) Supported by a Pyridine-Decorated Dianionic Ligand.

Abstract

Although synthesis, reactivity, and bonding of U(IV) and Th(IV) complexes have been extensively studied, direct comparison of fully analogous compounds is rare. Herein, we report corresponding complexes 1-U and 1-Th, in which U(IV) and Th(IV) are supported by the tetradentate pyridine-decorated dianionic ligand N2NN' (1,1,1-trimethyl-N-(2-(((pyridin-2-ylmethyl)(2-((trimethylsilyl)amino)benzyl)amino)methyl)phenyl)silanamine). Although 1-U and 1-Th are structurally very similar, they display disparate reactivities with TMS3SiK (tris(trimethylsilyl)silylpotassium). The reaction of (N2NN')UCl2 (1-U) and 1 equiv of TMS3SiK in THF unexpectedly formed [Cl(N2NN')U]2O (2-U) featuring an unusual bent U-O-U moiety. In contrast, a salt elimination reaction between (N2NN')ThCl2 (1-Th) and 1 equiv of TMS3SiK led to thorium complex 2-Th, in which the pyridyl group has undergone a 1,4-addition nucleophilic attack. Complex 2-Th serves as a synthon for preparing dimetallic bis-azide complex 3-Th by reaction with NaN3. The complexes were characterized by X-ray crystal diffraction, solution NMR, FT-IR, and elemental analysis. Computations of the formation mechanism of 2-U from 1-U suggest reduced U(III) as a key intermediate for promoting the cleavage of the C-O bonds of THF. The inaccessible nature of Th(III) as an intermediate oxidation state explains the very different reactivity of 1-Th versus 1-U. Given that reactants 1-U and 1-Th and products 2-U and 2-Th all comprise tetravalent actinides, this is an unusual case of very disparate reactivity despite no net change in the oxidation state. Complexes 2-U and 3-Th provide a basis for the synthesis of other dinuclear actinide complexes with novel reactivity and properties.